WO2011078639A2 - Obtention de graphène par oxydation en phase aqueuse - Google Patents

Obtention de graphène par oxydation en phase aqueuse Download PDF

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Publication number
WO2011078639A2
WO2011078639A2 PCT/MX2010/000152 MX2010000152W WO2011078639A2 WO 2011078639 A2 WO2011078639 A2 WO 2011078639A2 MX 2010000152 W MX2010000152 W MX 2010000152W WO 2011078639 A2 WO2011078639 A2 WO 2011078639A2
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WO
WIPO (PCT)
Prior art keywords
weight
graphite
exfoliation
oxidation
water
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PCT/MX2010/000152
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English (en)
Spanish (es)
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WO2011078639A3 (fr
Inventor
Erasto Armando Zaragoza Contreras
Sergio Gabriel Flores Gallardo
Rigoberto Ibarra Gomez
Claudia Alejandra Hernandez Escobar
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Centro De Investigacion En Materiales Avanzados, S.C.
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Application filed by Centro De Investigacion En Materiales Avanzados, S.C. filed Critical Centro De Investigacion En Materiales Avanzados, S.C.
Publication of WO2011078639A2 publication Critical patent/WO2011078639A2/fr
Publication of WO2011078639A3 publication Critical patent/WO2011078639A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation

Definitions

  • the present invention relates to the method of oxidation, intercalation and exfoliation of graphite (G) to obtain graphene sheets or nanometric plates.
  • This material is a semiconductor that can operate at nanometer scale and at room temperature, with properties that no other semiconductor offers and everything points to the possibility of creating new miniaturized electronic devices unsuspected with this material, being able to quickly approach the promising quantum computation, so that, predictably, all civilization will be favored.
  • Graphene is a material obtained from graphite, with the particularity that the first consists only of one of the sheets or plates that make up the second. That is, and to be located in the nanometric order to which we are referring: the graphene sheet is the thickness of "an"atom; regardless of the shapes and structures that can be acquired (for example, as nanotubes, if the sheet is rolled in the form of a cylinder, or as fullerenes, if the sheet is rolled up in the form of a balloon, or how many of these layers can be superimposed or combined to its applications and industrial uses
  • Graphene is derived primarily from an interleaving of graphite that can be converted to flexible graphite or graphene nanometer plates (PNG) .
  • a PNG is composed of a flat sheet of graphene or multiple flat sheets of stacked graphene and linked to each other
  • Each graphene plane also known as a graphene sheet or basal plane, comprises a two-dimensional hexagonal structure of carbon
  • the thickness of a PNG is 100 nanometers (nm) or smaller, being as thin as 0.34 nm for a single PNG sheet.
  • the length and width of a PNG are typically between 1 and 2 microns, but they could be longer or shorter. For certain applications, both the length and width must be less than 1 meter.
  • the so-called “heat method” has been used, which consists in applying a folded "adhesive tape" to the two ends of the workpiece. graphite, and then separating it and repeating the process several times until obtaining a single layer. All this (adhesive tape included) on a nanometric scale.
  • Graphene is a member of a broader family of structures in which carbon atoms join in flat sheets, forming a hexagonal honeycomb (with an atom in each vertex). Placed many honeycombs one on another, it has graphite.
  • the electrons interact with the graphene honeycomb and can move through hexagonal cells, at a speed only four hundred times lower than the speed of light, much higher than the usual electrons in an ordinary conductor, which is enough for exhibit relativistic behaviors.
  • electrons maintain this velocity even at very low temperatures by behaving as if they had no resting mass. Therefore, in order to study the physics of these electrons, it is necessary to use the Dirac equation for mass-free fermions.
  • Graphene acting as a stable and two-dimensional semiconductor allows electrons to move freely along the path that is most convenient, not attached to a straight path as in conventional transistors based on the semiconductor capabilities of silicon, which is used to create tiny tubes by where the electric current flows.
  • graphene electrons cannot be isolated in areas where they cannot leave.
  • graphene is a semiconductor that can operate at a nanometric scale and at room temperature, with properties that no other semiconductor offers and everything suggests that new miniaturized electronic devices unsuspected with this material can be created, allowing us to quickly approach the promising computing quantum, so, predictably all of civilization will be favorably affected.
  • US Patent Application 2008/0258359 describes a method for producing sheets or plates on a nanometric scale with thickness less than 100 nm; These plates are called graphenes.
  • the exfoliation of the plates is performed in aqueous medium with the assistance of ultrasound or some other method that provides high cutting efforts.
  • the addition of a surfactant is decisive to maintain the separation of the plates.
  • US patent application 2009/0028778 describes a process for graphite exfoliation to produce graphene plates or graphite nanogaleras.
  • the method comprises oxidation using carboxylic acids and hydrogen peroxide.
  • the plates thus obtained are in a thickness less than 30 nm.
  • US Patent 7,071,258 describes a process for obtaining graphene plates nanometric scale.
  • Graphene plates comprise from one sheet or multiplicity of graphite sheets.
  • Graphite is composed of a two-dimensional hexagonal network of carbon atoms and the plates have a magnitude of length, width and thickness of at least one of them less than 100 nm.
  • the production process comprises the following steps: a) partial or complete carbonization of a polymer precursor or heat treatment of petroleum or tar pitch to produce a polymeric carbon containing crystallites of micro and nanometric graphite scale, where each crystallite comprises a sheet or several flat sheets of graphite; b) exfoliation of crystallites in polymeric carbon; c) mechanical submission of polymeric carbon containing graphite exfoliated crystallites.
  • United States patent application 2005/0271574 describes a process for the production of graphene plates where each plate comprises from a sheet or multiplicity of graphite sheets.
  • the process : a) Provides a powder of fine graphite particles comprising graphite crystallites corresponding to a sheet or normally multiplicity of joined flat sheets of graphite; b) exfoliation of crystallites of graphites; and c) submission of mechanical wear in order to reduce at least one dimension of the particles on a nanometric scale, less than 100 nm.
  • Figure 1 is a graphical representation of unilayered graphene.
  • Figure 2 is a graphical representation of multilayer graphene.
  • Figure 3 is a scanning electron microscope micrograph showing graphene sheets or plates obtained by the inventors of this work, using the method of the present invention from commercial graphite.
  • Figure 4 is a micrograph with the thickness dimensions of graphene nanometer sheets or plates obtained during the development of the experimentation by the method of the present invention from commercial graphite.
  • Figure 5 is a scanning electron microscope micrograph showing graphene sheets or plates obtained by the method of the present invention from expanded graphite. Detailed description of the invention
  • the present invention relates to the method of oxidation, intercalation and exfoliation of commercial graphite or any kind of graphite (G) for obtaining graphene sheets or nanometric plates.
  • Said sheets or plates can be constituted in a thickness range between 0.34 to 100 nm, and with variable length and width, being able to reach nanometer magnitudes up to microns, the thickness dimension being more important as shown in Figure 4.
  • the material of heading is commercial graphite; however, expanded graphite or any other type can also be used.
  • an inorganic oxidizing agent of persulfate type also known as peroxydisulfate
  • metallic counterion of sodium (Na + ), potassium (K + ) or ammonium (NH4 + ) is used.
  • the oxidizing agent (AO) is used in a weight ratio to graphite (AO: G) from 0.1: 1 to 20: 1 weight / weight, preferably at a ratio of 1: 1 to 8: 1 weight / weight
  • Both materials may or may not be dry premixed before being integrated into a volume of water of 10 to 200 parts by weight relative to the weight of oxidizing agent; preferably from 25 to 50 parts by weight of water with respect to the weight of oxidizing agent is used.
  • the mixture produced is subjected to ultrasound for a time of 20 to 240 min, preferably for 60 to 120 min.
  • the sonification equipment can be a bath or a device with a lance, therefore, the frequency of sonification to perform the exfoliation can vary, depending on the equipment.
  • An intensive mixing device is also feasible to be used to facilitate exfoliation, although the use of ultrasound is more efficient.
  • Other methods such as the use of ball mills or mechanical wear may also be feasible for carrying out said process.
  • the oxidation is carried out within a temperature range of 15 to 150 ° C, preferably 30 to 70 ° C.
  • a surfactant is used, which can be of the anionic, cationic or non-ionic type.
  • the use of an anionic compound such as sodium dodecylbenzene sulphonate, sodium lauryl ether sulfate, sodium dodecyl sulfate, or any other preferably water soluble is recommended.
  • the concentration of the surfactant is in a concentration range of 1x10 " to 10 weight / weight with respect to water; preferably a weight / weight concentration of surfactant of lxl O " 3 to 0.1 with respect to the water content is used.
  • the method carried out step by step is the following: a) Graphite is placed in a container with an inorganic oxidizing agent of persulfate type (also known as peroxidi sulfate) with metallic counterion of sodium (Na + ), potassium (K + ) or ammonium (NH4 + ).
  • the oxidizing agent (AO) is used in a weight ratio to graphite (AO: G) from 0.1: 1 to 20: 1 weight / weight, preferably at a ratio of 1: 1 to 8: 1 weight / weight.
  • Both materials may or may not be dry premixed.
  • c) The material of a) is integrated at a volume of water of 10 to 200 parts by weight with respect to the weight of oxidizing agent; preferably from 25 to 50 parts by weight of water with respect to the weight of oxidizing agent is used.
  • the mixture produced in c) is subjected to ultrasound for a time of 20 to 240 min, preferably for 60 to 120 min.
  • the sonification equipment can be a bath or a device with a lance, therefore, the frequency of sonification to perform the exfoliation can vary, depending on the equipment.
  • An intensive mixing device is also feasible to be used to facilitate exfoliation, although the use of ultrasound is more efficient.
  • Other methods such as the use of ball mills or mechanical wear may also be feasible for carrying out said process.
  • the oxidation is carried out within a temperature range of 15 to 150 ° C, preferably 30 to 70 ° C.
  • the oxidation is carried out within a temperature range of 15 to 150 ° C, preferably 30 to 70 ° C.
  • a surfactant which can be of the ammonium, cationic or nonionic type.
  • an anionic compound such as sodium dodecylbenzene sulphonate, sodium lauryl ether sulfate, sodium dodecyl sulfate, or any other preferably water soluble is recommended.
  • the concentration of the surfactant is in a concentration range of 1x10 " to 10% weight / weight with respect to water; preferably a weight / weight concentration of surfactant of 1x10 " to 0.1 with respect to the water content is used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne le traitement d'oxydation, d'intercalation et d'exfoliation de graphite standard ou de graphite expansé, à l'aide d'agents oxydants inorganiques du type persulfate d'ammonium, potassium ou sodium, dans un milieu aqueux. Le produit de ce traitement, suite à l'analyse au microscope électronique, se présente sous forme de feuilles ou de plaques nanométriques de graphène dont l'épaisseur est inférieure à 100 nm.
PCT/MX2010/000152 2009-12-15 2010-12-13 Obtention de graphène par oxydation en phase aqueuse WO2011078639A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MXMX/A/2009/013701 2009-12-15
MX2009013701A MX2009013701A (es) 2009-12-15 2009-12-15 Obtencion de grafeno via oxidacion en fase acuosa.

Publications (2)

Publication Number Publication Date
WO2011078639A2 true WO2011078639A2 (fr) 2011-06-30
WO2011078639A3 WO2011078639A3 (fr) 2011-11-24

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WO (1) WO2011078639A2 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014089214A3 (fr) * 2012-12-04 2014-09-04 William Marsh Rice University Nanoparticules carbonées comme additifs d'amélioration de la conductivité pour des émulsions eau-dans-huile, émulsions eau-dans-huile et fluides de puits de forage à base d'huile
EP2964574A4 (fr) * 2013-03-08 2017-01-04 Garmor, Inc. Production de graphène oxydé à grande échelle pour des applications industrielles
US9828290B2 (en) 2014-08-18 2017-11-28 Garmor Inc. Graphite oxide entrainment in cement and asphalt composite
US9951436B2 (en) 2011-10-27 2018-04-24 Garmor Inc. Composite graphene structures
CN107973289A (zh) * 2017-11-08 2018-05-01 华侨大学 一种硫掺杂石墨烯催化材料及其制备方法
US10351711B2 (en) 2015-03-23 2019-07-16 Garmor Inc. Engineered composite structure using graphene oxide
US10535443B2 (en) 2013-03-08 2020-01-14 Garmor Inc. Graphene entrainment in a host
CN112194125A (zh) * 2020-10-21 2021-01-08 哈尔滨理工大学 天然鳞片石墨常压低温膨胀方法
US10981791B2 (en) 2015-04-13 2021-04-20 Garmor Inc. Graphite oxide reinforced fiber in hosts such as concrete or asphalt
US11038182B2 (en) 2015-09-21 2021-06-15 Garmor Inc. Low-cost, high-performance composite bipolar plate
US11214658B2 (en) 2016-10-26 2022-01-04 Garmor Inc. Additive coated particles for low cost high performance materials
US11482348B2 (en) 2015-06-09 2022-10-25 Asbury Graphite Of North Carolina, Inc. Graphite oxide and polyacrylonitrile based composite
US11791061B2 (en) 2019-09-12 2023-10-17 Asbury Graphite North Carolina, Inc. Conductive high strength extrudable ultra high molecular weight polymer graphene oxide composite

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GUOXIU WANG ET AL.: 'Synthesis and characterisation of hydrophilic and organophilic graphene nanosheets' CARBON vol. 47, 24 January 2009, pages 1359 - 1364 *
MUSTAFA LOTYA ET AL.: 'Liquid Phase Production of Graphene by Exfoliation of Graphite in Surfactant/Water Solutions' JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 131, no. 10, February 2009, pages 3611 - 3620 *
WUFENG CHEN ET AL.: 'Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves' CARBON vol. 48, 26 November 2009, pages 1146 - 1152 *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10815583B2 (en) 2011-10-27 2020-10-27 Garmor Inc. Composite graphene structures
US11466380B2 (en) 2011-10-27 2022-10-11 Asbury Graphite Of North Carolina, Inc. Composite graphene structures
US9951436B2 (en) 2011-10-27 2018-04-24 Garmor Inc. Composite graphene structures
EP2928817A4 (fr) * 2012-12-04 2016-09-07 Univ Rice William M Nanoparticules carbonées comme additifs d'amélioration de la conductivité pour des émulsions eau-dans-huile, émulsions eau-dans-huile et fluides de puits de forage à base d'huile
WO2014089214A3 (fr) * 2012-12-04 2014-09-04 William Marsh Rice University Nanoparticules carbonées comme additifs d'amélioration de la conductivité pour des émulsions eau-dans-huile, émulsions eau-dans-huile et fluides de puits de forage à base d'huile
US11098233B2 (en) 2012-12-04 2021-08-24 William Marsh Rice University Carbonaceous nanoparticles as conductivity enhancement additives to water-in-oil emulsions, oil-in-water emulsions and oil-based wellbore fluids
US10995002B2 (en) 2013-03-08 2021-05-04 University Of Central Florida Research Foundation, Inc. Large scale oxidized graphene production for industrial applications
US9758379B2 (en) 2013-03-08 2017-09-12 University Of Central Florida Research Foundation, Inc. Large scale oxidized graphene production for industrial applications
US20190152785A1 (en) * 2013-03-08 2019-05-23 University Of Central Florida Research Foundation, Inc. Large Scale Oxidized Graphene Production for Industrial Applications
US10535443B2 (en) 2013-03-08 2020-01-14 Garmor Inc. Graphene entrainment in a host
US11361877B2 (en) 2013-03-08 2022-06-14 Asbury Graphite Of North Carolina, Inc. Graphene entrainment in a host
US10287167B2 (en) 2013-03-08 2019-05-14 University Of Central Florida Research Foundation, Inc. Large scale oxidized graphene production for industrial applications
EP2964574A4 (fr) * 2013-03-08 2017-01-04 Garmor, Inc. Production de graphène oxydé à grande échelle pour des applications industrielles
US10351473B2 (en) 2014-08-18 2019-07-16 Garmor Inc. Graphite oxide entrainment in cement and asphalt composite
US9828290B2 (en) 2014-08-18 2017-11-28 Garmor Inc. Graphite oxide entrainment in cement and asphalt composite
US10351711B2 (en) 2015-03-23 2019-07-16 Garmor Inc. Engineered composite structure using graphene oxide
US10981791B2 (en) 2015-04-13 2021-04-20 Garmor Inc. Graphite oxide reinforced fiber in hosts such as concrete or asphalt
US11482348B2 (en) 2015-06-09 2022-10-25 Asbury Graphite Of North Carolina, Inc. Graphite oxide and polyacrylonitrile based composite
US11038182B2 (en) 2015-09-21 2021-06-15 Garmor Inc. Low-cost, high-performance composite bipolar plate
US11916264B2 (en) 2015-09-21 2024-02-27 Asbury Graphite Of North Carolina, Inc. Low-cost, high-performance composite bipolar plate
US11214658B2 (en) 2016-10-26 2022-01-04 Garmor Inc. Additive coated particles for low cost high performance materials
CN107973289A (zh) * 2017-11-08 2018-05-01 华侨大学 一种硫掺杂石墨烯催化材料及其制备方法
US11791061B2 (en) 2019-09-12 2023-10-17 Asbury Graphite North Carolina, Inc. Conductive high strength extrudable ultra high molecular weight polymer graphene oxide composite
CN112194125A (zh) * 2020-10-21 2021-01-08 哈尔滨理工大学 天然鳞片石墨常压低温膨胀方法

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Publication number Publication date
MX2009013701A (es) 2011-07-01
WO2011078639A3 (fr) 2011-11-24

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